Laser verification and authentication Raman spectrometer (LVARS) detecting the stokes and/or anti-stokes emission

ABSTRACT

The LVARS is a fully instrumental, non-destructive spectroscopic device for the analysis and verification and authentication of the optical and electromagnetic properties (OEMP) of organic or inorganic media that is either naturally occurring, or manufactured or processed such as the inks, dyes, thin films, plastics, toners, paper, fixatives, paints, and printing agents used in documents and financial instruments. The instrument is quantitative in nature so as to correlate compositional data (elemental, isotopic, structure) with Raman optical spectra. The LVARS design consists of a computer-controlled spectrometer with a microscope-guided grid head containing the laser excitation source and detector and optics. The spectrometer contains signal processing electronics which sends a stream of data to the computer for analysis and correlation with the library database. 
     In other embodiment, the LVARS system is also capabable of performing analysis and verification and authentication of the OEMP of organic and inorganic compounds, for both natural as well as manufactured compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of patent application Ser. No. 09/270,415filed on Mar. 16, 1999, now Pat. No. 6,008,888, issued Dec. 28, 1999,which is commonly assigned herewith to The Wizard of Ink & Co., andwhich is incorporated hereinto in its entirety by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention disclosed broadly relates to the field of spectroscopicanalysis, and more particularly relates to the field of Ramanspectroscopic analysis (both qualitative and quantitative) for theauthentication of the optical and electromagnetic properties of anynaturally occurring or manufacture or processed occurring ormanufactured or processed media that is organic or inorganic such asinks, dyes, thin films, plastics, toners, paper, fixatives, paints,printing agents and other written materials. The invention disclosedalso broadly relates to the field of Raman spectroscopic analysis forthe authentication of the optical and electromagnetic properties oforganic and inorganic compounds, for both natural as well asmanufactured materials.

2. Description of the Related Art

The investigation of authenticity, and in particular, the discovery of aforgery, are problems that have plagued man since antiquity. One earlytarget of forgery was currency and many laws were passed to thwartcounterfeiting. Today, fraudulent activity encompasses much more thanpaper currency. It can include business and legal documents, creditcards, checks, other financial media, art, antiquity materials, anddocumented security threats to person(s) and/or institutions.

The loss of valuable resources, man-hours, and associated assets due tofraudulent documents and financial media are escalating daily in theUnited States and other parts of the world. Part of the problem is thatthere are no predominantly established, widely accepted protocolsbetween government agencies, business, and academia to proveauthenticity. The primary difficulty stems from a lack of aninstrumental solution. Currently there is no automated mechanism ormethod to analyze documents or financial media which takes into accountaccurate age-dating, the precise matching of varying ink samples, andalteration of a genuine article. Every year, hundreds of thousands ofworking hours are devoted to analyzing documents and financial media inorder to curb the billions of dollars of losses in the domestic andinternational markets. The incurred monetary loss is mainly due tocheck, credit card, and paper currency fraud.

Unfortunately, technology which is available to the average consumercontinues to remain on par with the processes used to create originalfinancial media and assorted legal documentation by both government andcorporations. Color copiers, scanners, multimedia software, laserprinters, and desktop publishing software are among the tools whichmodern day criminals can use to create a forgery. Local, state, andfederal law enforcement agencies as well as financial institutions arecalling for an automated mechanism or method by which the expedientauthentication of legal and financial documents, and documentsthreatening persons or institutional security can be established.Accordingly, a need exists to provide a method and system to aid in theverification of documents and other media.

Historically, a variety of techniques have been used for the analysis ofinks, dyes, thin films, plastics, and written materials. One easytechnique to thwart counterfeiting was the use of multicolor printing.This technique, although useful, is not without its shortcomings. Thewide availability of color printers and especially full color copiershas greatly reduced the effectiveness of multicolor printing to stemcounterfeiting.

Other techniques for the analysis of inks, dyes, thin films, plastics,and written materials are adaptations of classical wet chemistryanalysis where a document or ink sample is subjected to a variety ofsolvents and chemically reactive agents. These chemical reactions arethen compared to a known sample using the human eye and microscopicexamination. Other forms of wet chemistry analyses involve spot tests oninks and documents which incorporate a light source to excite variouschemicals. While useful, these classical wet chemistry analyses sufferfrom several shortcomings.

First, these classical wet chemistry analyses have proven to be highlyunreliable as they involve personal, subjective judgements; even theopinions of experts may vary from one to another. Second, thesetechniques can not accurately distinguish between different samples ofink. Third, the use of wet chemistry techniques can not age-date withina single sample of ink. Fourth, these techniques do not provide a methodto determine the origin of the document. Fifth, the use of these wetchemistry techniques is destructive and therefore makes the analysisdifficult to repeat when necessary. Destructive techniques are highlyundesirable, especially for application on rare or historic documents,and on evidence used in trials. Sixth, the use of classic wet chemistryis cumbersome because it requires hand-to-sample manipulation. A widerange of chemical tests have been developed during this century, butnone have proven accurate over a range of samples. Most of these testsare microscale. This makes them difficult to perform, difficult torepeat, destructive in almost all cases, and subject to wide variety ofenvironmental contamination. Seventh, few forensic methods have beendeveloped to calibrate these tests. For example, thin-layerchromatography (TLC) has been used to analyze very small flakes of inkand dyes, but this technique, at best, is merely qualitative, notquantitative. Eighth, and perhaps most important, forgers have developedtechniques to overcome wet chemistry analysis.

Inks, dyes, thin films, plastics, and written materials can be analyzedusing automated comparison which incorporates spectral analysis usinglight sources of different wavelengths. However, this suffers fromseveral major problems: wavelengths are polychromatic, energy is eithertoo high or too low and the final examination has to be done by eyesightonce again. Even when the best light sources are used, such as lasers,in conjunction with the best detectors, the results are stillqualitative, not quantitative, due to damage to the sample fromanalysis, or the lack of any standards for comparison. Moreover, thecurrent spectral analysis of credit cards suffers from severalweaknesses. There is the destruction of the sample as well as theinability to differentiate between a genuine card and a genuine cardthat has been altered (as opposed to a total forgery). Document analysishas attempted to develop techniques for age dating using basicchemistry, but this is simply not sophisticated enough.

One technique for the analysis of inks, dyes, thin films, plastics, andwritten materials is scanning electron microscopy-electron diffractionx-rays (SEM-EDX). The technique of SEM-EDX overcomes some of theproblems with earlier techniques, but still suffers from shortcomings.First, SEM-EDX is not accurate due to a wide variety of environmentalcontamination such as particulate matter. This contamination interfereswith the accurate microscopic compositional sample determination.Second, with SEM-EDX, there is almost no spatial accuracy for differingelemental concentrations at the sub-micron level. Third, althoughSEM-EDX is used to determine specific elements present qualitatively,the SEM-EDX technique cannot distinguish on a small scale the preciselocation of a quantitative amount. Fourth, SEM-EDX cannot determineorganic species, which comprises the majority of the samples used indocument authentication and financial instruments.

Another technique for the analysis of inks, dyes, thin films, plastics,and written materials is magnetic ink character recognition (MICR)analysis. However, MICR cannot be used for the analysis of financialmedia and many identification systems because such documentation usesstrips of magnetic material for information storage. An analysisconducted using MICR would destroy stored material within the magneticstrip, and in turn, the magnetic material would provide questionableresults.

Recently, a new technique incorporating Raman spectroscopy has been usedfor the analysis of art work, ancient documentation, as well as morerecently printed material. The Raman analysis of art has not yet provenitself quantitative nor has it been optimized for non-metallic species(organic). In addition, current Raman technology developed specificallyfor the analysis of inks and dyes (FNF Foram 6500) is also incapable ofquantitative analysis, possibly destructive, and subject to fluorescenceand back-scattering interference.

The main problems that all previously mentioned techniques suffer fromare an inability to yield quantitative measurements in either elementalor molecular analysis, a destruction of evidence, the inability todetermine that degree of destructiveness, and the inability todistinguish between molecular or oxidation states which makes ageverification and artificial aging detection by photolysis or heatimpossible. These techniques are inaccurate because their producedresults are not quantitative. They are cumbersome in that they requirehand-to-sample manipulation on written words and because they lackspectroscopic inter-comparison. Hence, the need exists for an apparatusto perform a quantitative, non-destructive, accurate, precise(reproducible across a range of organic or inorganic media that iseither naturally occurring, or manufactured or processed such assamples), elemental and molecular specific, analysis of inks, dyes, thinfilms, plastics, toners, papers, fixatives, paints, printing agents, andother written materials.

SUMMARY OF THE INVENTION

The LVARS system is a fully instrumental, non-destructive spectroscopicdevice for the analysis and verification and authentication of theoptical and electromagnetic properties (OEMP) of organic or inorganicmedia that is either naturally occurring, or manufactured or processedsuch as inks, dyes, thin films, plastics, toners, paper, fixatives,paints, and printing agents used in documents, financial instruments,art, and more. The LVARS system is quantitative in nature so as tocorrelate compositional data (elemental, isotopic, structure) with Ramanoptical spectra. The LVARS system consists of a computer-controlledspectrometer with a microscope-guided grid head containing the laserexcitation source and detector and optics. The spectrometer containssignal processing electronics which sends a stream of data to thecomputer for analysis and correlation with the library database.

In other embodiments, the LVARS system is also capabable of performinganalysis and verification and authentication of the OEMP of organic andinorganic compounds, for both natural as well as manufactured compounds.

BRIEF DESCRIPTION OF THE DRAWINGS

The subject matter which is regarded as the invention is particularlypointed out and distinctly claimed in the claims at the conclusion ofthe specification. The foregoing and other objects, features, andadvantages of the invention will be apparent from the following detaileddescription taken in conjunction with the accompanying drawings.

FIG. 1 is an elevational view of the LVARS system according to thepresent invention.

FIG. 2 is a cross-sectional bottom view of the examination module ofFIG. 1 taken along axis X—X= showing the movable grid head assemblyaccording to the present invention.

FIG. 3 is a cross sectional side view of the movable grid head of FIG. 1taken along the axis Y—Y= according to the present invention.

FIG. 4 is a block diagram of the major components of the spectrometerapparatus FIG. 1 according to the present invention.

FIG. 5 is a block diagram of the movable grid head of FIG. 2 accordingto the present invention.

FIG. 6 is a flow diagram of the process performed by the LVARS systemaccording to the present invention.

DETAILED DESCRIPTION OF AN EMBODIMENT

However, it should be understood that these embodiments are onlyexamples of the many advantageous uses of the innovative teachingsherein. In general, statements made in the specification of the presentapplication do not necessarily limit any of the various claimedinventions. Moreover, some statements may apply to some inventivefeatures but not to others. In general, unless otherwise indicated,singular elements may be in the plural and visa versa with no loss ofgenerality.

Turning to the figures, where like references refer to throughoutseveral drawings, shown in FIG. 1 is an elevational view of an LVARS(Laser Verification and Authentication Raman Spectrometer) system 100according to the present invention. The LVARS system 100 consists of aspectrometer apparatus 102 connected to a computer controller 120. Thecomputer controller 120 is a general purpose computer such as a laptopwith standard interfaces such as a parallel port, serial communications,and network communications. In the computer controller 120, allprocessing and control programming is contained as well as a librarydatabase 122. The spectrometer apparatus 102 is designed to be portable.In one embodiment, the spectrometer apparatus 102 is approximately 30″in length by 30″ in width by 25″ in height, so that it can easily betransported from one location to another. Two access ports 104 are shownfor accessing the internal components that will be discussed in FIG. 4below. The spectrometer is constructed with any nonmagnetic material,that is chemically non-reactive and can be coated with a black powdercoat finish so as to be non-spectroscopically active. One example of anonmagnetic, chemically inert and non-spectroscopically active materialis black anodized aluminum. The entire spectrometer apparatus 102 issupported by antivibration legs 108 such as pneumatic legs or similarsupports. A variety of ports are coupled to the spectrometer apparatus102 for interfacing to devices, such as a power port 110 for interfacingto an external power source; a data port 112 and a controller port 114for communicating with computer controller 120. Although the computercontroller 120 is a general purpose computer, it will be understood tothose skilled in the art, that any processor based system can be used.Moreover, it is important to note, that these dimensions are exemplaryonly, and it will be understood to those skilled in the art, thatchanges can be made to the dimensions of the device without departingfrom the true scope and spirit of the invention

FIG. 2 is a cross-sectional bottom view of the spectrometer apparatus102 of FIG. 1 taken along axis X—X= showing the movable grid headassembly 210 according to the present invention. The entire spectrometerapparatus 102 forms a substantially rectangular chamber 212 in which asample can be introduced into the chamber 212 through access door 202.An x-y table 204 with nanometer resolution, such as those available fromAnorad Corporation or Burleigh Instrument Corporation is attached to thetop inner side 214 of the spectrometer apparatus 102. In thisembodiment, the linear area for both the x and y axis travel is about0.6 meters, but other dimensions made be used. The movable grid assembly210 is fastened to x-y table 204 so that it may be positioned by the x-ytable 204. A cable feed 216 for carrying data communications, controland power connects the spectrometer apparatus 102 to the movable gridhead assembly 210 and the x-y table 204.

Referring to FIG. 3, shown a cross sectional side view of the movablegrid head assembly 210 of FIG. 1 taken along the axis Y—Y= according tothe present invention. The spectrometer apparatus 102 supported by legs108 with expandable side walls 304 for accommodating samples up toapproximately 12″ in height. The side walls, 304, the top under side 214of the spectrometer apparatus 102 and a sample platen 302 form thesubstantially rectangular chamber area 212 which is isolated fromambient light to enable analysis of a specimen placed inside the cavity212 via the access door 202. It should be understood to those skilled inthe art that many mechanical configurations of the spectrometerapparatus 102 are possible to define a chamber 212 comprising of avariety of different geometric dimensions and shapes for analysis ofsamples is within the true scope and spirit of the present invention.

The spectrometer apparatus 102 is described in further detail. Referringto FIG. 4 there is shown a block diagram 400 of the major components ofthe spectrometer apparatus 102 of FIG. 1 according to the presentinvention. A computer bus 402 such as a standard IBM Personal ComputerBus, a VME Bus, IEEE 488 Bus or equivalent acts as the controllerbackbone for the components in the LVARS system 100. As described inFIG. 1 above, a variety of ports 110, 112 and 1 14 interface to thecomputer bus 402 for communicating with computer controller 120. Astabilized power unit with feedback control 404 powers the components inthe LVARS system 100. One typical stabilized power unit with feedbackcontrol 404 is available from LeCroy or EG&G. A multiple wavelengthRaman laser head supply 406 with diode lasers such as those supplied byCoherent or Spectra Physics, provides tunable multiple wavelengthoutput. The Raman laser head supply produces different wavelengths viasolid state diodes, which are chosen for their small size, low powerrequirement, low power output, and ease of maintenance. The mainstrengths of Raman spectroscopy in the LVARS system 100 are theexcellent specificity (both elemental or in-situ molecular), excellentspatial resolution, excellent sensitivity, and strong immunity tointerference especially fluorescence. In this embodiment, the laser headsupply 406 provides a range of the wavelengths from 200 nanometers up to2000 nanometers. A computer controlled 360 degree translation stagemounted beam splitter and mirror 408 is coupled to laser head supply406. The beam splitter and mirror 408 split the laser output from laserhead supply between a laser beam power meter 410 and a laser lightoutput-to-fiber coupler 412. One example of the laser beam power meter410 is available from Burleigh or Coherent. The laser beam power meter410 enables the laser output, including the laser power, laser beamprofile and laser waveform from laser head supply 406 to be monitoredvia computer bus 402. The laser light output-to-fiber coupler 412provides laser output to movable grid assembly 210. A cable feed 414holds a combination of several types of cables (fiber optic data lines,control lines, power lines, and cooler lines) for movable grid assembly210. First, fiber optic data lines include: the laser lightoutput-to-fiber coupler 412 from laser head supply 406 and microscopeview 416 coupled to a Zeiss brand microscope 420 or equivalent. Second,control lines include: microscopic control cables 418 from microscope420 for controlling the focus of the microscope view and detector datalines 422 from the multiple detectors in the movable grid head assemblywhich will be discussed in further detail below. The detector data lines422 are connected to the box car integrator 424 for combining the dataon detector data lines 422. It is important to point out the multipledata paths to integrator 424. The integrator 424 is a boxcar typeintegrator such as those available from Stanford Research Systems orequivalent. The integrator 424 is coupled to a laser correlator 426 forproviding a correlative feedback to laser supply 406. This enables thelaser supply 406 to be adjusted to give a desired output as read by thedetectors for a given laser wavelength, power and beam profile. Athermo-electric cooler 428 is coupled to the detectors in the movablegrid head assembly 210 for maintaining the detectors in a predeterminedoperating temperature range. In this embodiment, the predeterminedoperating range is between −200 and +40 degrees centigrade and a OxfordSystems brand thermo-electric cryostat or equivalent is used.

It is important to note that this embodiment is exemplary only and thatmany changes are possible to the above configuration without departingfrom the true scope and spirit of the invention. In particular,adaptations to the above include (i) changes in the standard size of thechamber 212 to accommodate different samples; (ii) other hardware andsoftware can be substituted in place of the computer bus 402, as thecontroller backbone for the components in the LVARS system 100; (iii)any number of ports 110, 112, 114 can be used depending on theconfiguration of the LVARS system 100; (iv) laser 402 with better orequivalent capabilities; and the functions of the boxcar integrator 424can be implemented in many combinations of hardware and software.

FIG. 5 is a block diagram 500 of the major components of the movablegrid head assembly 210 of FIG. 2 according to the present invention. Alaser output head assembly 502 and a detector head assembly 512 areslidably mounted on an arc-shaped track 520. A pair of servo controlledmotors 522 enables the output head assembly 502 and the detector headassembly 506 to be individually positioned anywhere along the arc-shapedtrack 520. This ability to independently position both the output headassembly 502 and the detector head assembly 512 provides a range ofadjustment between 0° and 180° for the angle of analysis θ. As shown inFIG. 5, the angle of analysis θ is defined by the angle of incidence θ₁plus the angle of reflection θ₂. Stated mathematically, the angle ofanalysis is θ=θ₁+θ₂ where line L is perpendicular to sample 510 restingon sample platen 302 of spectrometer apparatus 102. Accordingly, theangle of analysis θ corresponds to the output 504 of output headassembly 502 and the laser emissions 506 to sample 510, and the Ramanspectra 508 from 510 and can be adjusted such that 0°≦θ≦180°. Themounting method shown in FIG. 5 is exemplary only and otherconfigurations are possible to provide an adjustable angle of incidenceθ.

The output head area 502 is coupled to the laser light output-to-fibercoupler 412 from the Raman laser head supply 406. The output 504 oflaser head assembly 502 is focused on sample 510 using a computercontrolled lens 504. The Raman spectra 508 are directed by holographicgrating 514 and are detected by detectors 416. The holographic grating514 filters scattered light and any other device which can separatelight based on its wavelength and energy, may be used in place of aholographic grating without departing from the spirit and scope of thepresent invention. The detectors 416 are comprised of multipledetectors. These detectors 416 include: a real-time-full frame chargecouple detector (CCD) which is available from EG&G; a photo-multipliersuch as those available from Hamamatsu; an infrared InGaAs or similar;and a Ge(HPGe/Si(Li)) detector or similar from Oxford Systems. Acomputer controller preamp 418, such as Hamamatsu, is connected to theconnector heads 416 prior to being fed to integrator 424. The integrator424 rejects scattering and fluorescence signals which mask the Ramanspectra. In addition, the integrator 424 is coupled to the laser supply406 through laser correlator 426 to enable both spatial and temporalresolution to be correlated. A computer controlled aperture 524 isconnected to visible light microscope 420. A set of computer controlledwhite lights 528 or light ring with adjustable light intensity isincluded for manual observation with the eye to ensure accurate laserhead assembly 502 and detector head 512 alignment. The use of a veryaccurate x-y positioner, combined with a very accurate laser headassembly 502 and detector head 512 alignment enables accurate spotplacement and analysis sizes on the order of 0.10 to 1.0 micrometers. Inan alternate embodiment, a CCD camera is coupled to the microscope toenable the display of the sample 510 being analyzed on a monitor (notshown). The detector head 512 of the LVARS system 100 combined with thevery accurate positioning delivers a high resolution Raman signal. Thespectral range of the detectors 416 in the detector head 512 are 200 to8,000 cm⁻ with a spectral resolution from 0.05 cm⁻¹ to 10.00 cm⁻¹. Withmultiple laser excitation sources from 200 to 2000 nm and multipledetectors internal to the instrument, the LVARS has great flexibility toanalyze varying samples 510. It will be understood to those skilled inthe art, the movable detector grid head 210 of the LVARS system 100 hascomplete spatial resolution control. In addition, computer controller120 guides and monitors Raman excitation head 406, optics 504,microscope 420 and movable grid head assembly 210 functions in thespectrometer LVARS system 100.

Referring now to FIG. 6 is shown a flow diagram of the process performedby the LVARS system 100. The process begins with reading the backgroundspectra of the chamber without a laser and all the detection devicesturned on, step 602. These detection devices include the microscope 420with lights 528 shut off and detectors 416 in detector head assembly512. This value should be negligible and the value is stored in thecomputer database 122 for subtraction later. If there is backgroundspectra measured over a certain threshold, a determination must be madeif the background spectra is from the equipment of the LVARS system 100itself such as a camera (not shown) or detector head assembly 512. Next,in step 604, an unknown sample 510 is placed into sample chamber 212 ofthe spectrometer apparatus 102. In step 606, the background spectrum istaken without turning on the laser output 506 in laser output headassembly 502 and turning on all the detection devices. Typically thisbackground spectra should be negligible as measured with all detectordevices. As before in step 602, if there is background spectra measuredover a certain threshold for the type of sample entered in the database122, a determination must be made if the background spectra is from theequipment of the LVARS system 100 itself such as a camera (not shown) ordetector head assembly 512 or the sample 510 itself. There are methodsknown to determine the source of the background spectra. It should benoted that some samples give off phosphorescence that can interfere withthe Raman signal 508 from the sample 510. The sample region may have tobe selected if the paper gives off phosphorescence. The grid headassembly 210 may have to be positioned to a very small region using x-ypositioning apparatus 204. For example, suppose the sample 510 isprinted ink on paper and the paper phosphoresces. This is common withrecycled paper. The area of analysis of the grid head assembly may haveto be narrowed to one character or even portion of a character for theprinted ink to avoid measurements masked by the paper on the sample 510.The background spectra of the sample may be mathematically integrated oncomputer 120 for analysis and subtraction later. Information on thebackground spectra of the sample is also used to scan the database 122for similar known samples.

When the sample 510 is placed in the sample chamber, information isentered into the LVARS system 100 regarding the type of sample to betaken, for example, ink, paper, and any other sample properties known,step 608. In addition, in step 608, any physical and chemical propertiesare entered in computer 120. All these known quantities are stored indatabase 122 of computer system 120. At this point, the computer 120begins scanning the database 122 for known samples with similarproperties, step 610.

Next the laser irradiation of sample 510 begins, step 612. The strengthof the irradiation signal 508 from sample 510 varies widely. If thereare known samples matched in the database from the steps above, thisinformation is used to set the laser 406 settings, step 614. If thesample 510 does not match any known samples stored in the database, thenmicroscopic alignment on the sample is made for the target area, step616, and a series of scans begins from low energy (long wavelength) tohigh energy (short wavelength) using the tunable laser 406, while allthe detectors 512 are turned on, step 618. When the Raman spectra regionof highest activity is found, the detectors 512 and the associatedpreamp 418 and amplifier 432 settings are optimized, step 620. Theoptimization consists of adjusting the amplification for the detectors512. The less amplification from the detectors 416 that is needed, theless possibility of injecting unwanted noise into the signal ordegrading the signal-to-noise ratio from the detector. The Raman spectrais sampled, transformed, and stored, step 622, where the Raman spectraincludes at least one Stokes or Anti-Stokes component or a combinationthereof.

The boxcar integrator correlated to the wavelengths of laser 406,examines both the laser signal as well as the background spectra fromstep 612 and performs an integration, amplification, and conditioning,of the signal, steps 624. The functions in step 624, comprises andmathematical manipulations of the Stokes and/or Anti-Stokes components.The integration and amplification allows for a signal to be detecteddifferent from the laser so as to account for any harmonics that may bepresent from the detectors 416.

Steps 626 and 628 performs analysis on computer 120 using the databaselibrary 122. Additional spectra are sampled to confirm or disprovequestioned peaks and/or compounds based on library recommendations, step630. The computer analysis takes the known information input in duringstep 616 such as whether paper and ink are being analyzed or toner onpaper is being examined. This greatly reduces the amount of data indatabase 122 that has to be reviewed. Other types of data includes thetypes of papers, inks, dyes, toners, thin films, plastics, fixatives,paints, and printing agents used in documents and financial instrumentsand other printed materials. It is important to note that the type ofdata includes organic and inorganic compounds, as well as materialsoccurring naturally or that are manufactured.

The analysis includes Raman optical spectra correlated to compositionaldata (elemental, isotopic, structure), step 632. The analysis includescomparing the sample and its known quantities against previously entereddata of correlated spectra in the database 122, step 616. The librarydatabase 122 consists of the correlated Raman spectra of previouslyanalyzed reference specimens: their Raman spectra, their magneticsusceptibility, absolute elemental and isotopic composition, NMR(Nuclear Magnetic Resonance), molecular structure data, and massspectral molecular identity. If no Raman spectra are available forcomparison, the signal can be stored in database 122 as a new entryalong with the other known properties entered in step 608 above.Finally, the output can be directed to a variety of devices includingthe database 122, video display on the computer 120 or equivalent, step634. The LVARS system 100 can non-destructively evaluate thermal andphotolysis effects for age dating by examining electronic bonding states(oxidation) and molecular decomposition products. The LVARS avoids beingcumbersome by instrumentally manipulating the sample. Finally, the LVARScan determine document origin by chemically matching the daughterproducts to the apparent source.

Although a specific embodiment of the invention has been disclosed, itwill be understood by those having skill in the art that changes can bemade to this specific embodiment without departing from the spirit andscope of the invention. The scope of the invention is not to berestricted, therefore, to the specific embodiment, and it is intendedthat the appended claims cover any and all such applications,modifications, and embodiments within the scope of the presentinvention.

What is claimed is:
 1. A method to analyze media for composition andauthentication of a source of unknown media comprising the steps of:exposing a sample of unknown media simultaneously to multiplewavelengths of a Raman laser source; reading a Raman spectra of thesample of the unknown media through a variety of detectors each with aspecific wavelength detection region using Raman spectroscopy, whereinthe Raman spectra comprises at least one Stokes component and/or atleast one Anti-Stokes component; and manipulating mathematically atleast one of the Stokes component and/or at least one of the Anti-Stokescomponent.
 2. The method according to claim 1, wherein the step ofreading a Raman spectra includes reading a Raman spectra comprising atleast one Stokes component and at least one Anti-Stokes component. 3.The method according to claim 2, wherein the step of manipulatingmathematically includes manipulating at least one of the Stokescomponent and at least one of the Anti-Stokes component.
 4. The methodaccording to claim 1, wherein the step of exposing a sample of unknownmedia includes exposing a sample of unknown media which is organic. 5.The method according to claim 1, wherein the step of exposing a sampleof unknown media includes exposing a sample of unknown media which isinorganic.
 6. The method according to claim 1, wherein the step ofexposing a sample of unknown media includes exposing a sample of unknownmedia which is naturally occurring.
 7. The method according to claim 1,wherein the step of exposing a sample of unknown media includes exposinga sample of unknown media which is manufactured.
 8. A method to verifythe origin of an unknown sample comprising the steps of: exposing asample of an unknown media to a multiple wavelength laser source inorder to create Raman emissions from the sample; detecting the Ramanemissions from the sample using one or more detectors, wherein the Ramanemissions comprises at least one Stokes component and/or at least oneAnti-Stokes component; and comparing the detected Raman spectra withRaman spectra previously stored in a database.
 9. The method accordingto claim 8, further comprising the step of: manipulating mathematicallyat least one of the Stokes component or at least one of the Anti-Stokescomponent.
 10. The method according to claim 8, wherein the step ofdetecting the Raman emissions includes detecting the Raman emissionscomprising at least one of the Stokes component and at least one of atleast one Anti-Stokes component.
 11. The method according to claim 10,wherein the step of detecting the Raman emissions includes detecting theRaman emissions and manipulating a combination of one or more of theStokes component and at least one or more of the Anti-Stokes component.12. The method according to claim 8, wherein the step of exposing asample includes exposing a sample of an unknown media which is organic.13. The method according to claim 8, wherein the step of exposing asample includes exposing a sample of an unknown media which isinorganic.
 14. The method according to claim 8, wherein the step ofexposing a sample includes exposing a sample of an unknown media whichis naturally occurring.
 15. The method according to claim 8, wherein thestep of exposing a sample includes exposing a sample an of unknown mediawhich is manufactured.
 16. A computer readable medium containing programinstructions for verifying the origin of an unknown sample, said programinstructions comprising instructions for: exposing a sample of anunknown media simultaneously to multiple wavelengths of Raman lasersource; reading a Raman spectra of the sample of the unknown mediathrough a variety of detectors each with a specific wavelength detectionregion using Raman spectroscopy, wherein the Raman spectra comprises atleast one Stokes component and/or at least one Anti-Stokes component;and manipulating mathematically at least one of the Stokes componentand/or at least one of the Anti-Stokes component.
 17. The computerreadable medium of claim 16, wherein the programming step of reading aRaman spectra includes reading a Raman spectra comprising at least oneStokes component and at least one Anti-Stokes component.
 18. Thecomputer readable medium of claim 17, wherein the programming step ofmanipulating mathematically includes manipulating at least one of theStokes component and at least one of the Anti-Stokes component.
 19. Thecomputer readable medium of claim 16, wherein the programming step ofexposing a sample of an unknown media includes exposing a sample ofunknown media which is organic.
 20. The computer readable medium ofclaim 16, wherein the programming step of exposing a sample of anunknown media includes exposing a sample of unknown media which isinorganic.
 21. The computer readable medium of claim 16, wherein theprogramming step of exposing a sample of an unknown media includesexposing a sample of unknown media which is naturally occurring.
 22. Thecomputer readable medium of claim 16, wherein the programming step ofexposing a sample of an unknown media includes exposing a sample ofunknown media which is manufactured.
 23. A system for verifying theorigin of an unknown sample comprising: a chamber for exposing thesample simultaneously to a multiple wavelength Raman laser source inorder to create Raman emissions from the sample; two or more detectorseach with a specific wavelength detection region for detecting the Ramanspectra, wherein the Raman spectra comprises at least one Stokescomponent and/or at least one Anti-Stokes component; and a computer formanipulating mathematically at least one of the Stokes component and/orat least one of the Anti-Stokes component.
 24. The system according toclaim 23, wherein the two or more detectors detect Raman spectracomprising at least one Stokes component and at least one Anti-Stokescomponent.
 25. The system according to claim 24, wherein the computermanipulates at least one of the Stokes component and at least one of theAnti-Stokes component.
 26. The system according to claim 23, wherein thesample of unknown media is organic.
 27. The system according to claim23, wherein the sample of unknown media is inorganic.
 28. The systemaccording to claim 23, wherein the sample of unknown media is naturallyoccurring.
 29. The system according to claim 23, wherein the sample ofunknown media is manufactured or processed.